Silver halide photographic materials

ABSTRACT

Photosensitive materials which have a high speed and which exhibit little pressure desensitization and pressure fogging are obtained by means of this invention.

FIELD OF THE INVENTION

This invention concerns silver halide photographic materials and, moreprecisely, it concerns silver halide photographic materials which havehigh speed and gradation, and which have excellent pressure resistingproperties.

BACKGROUND OF THE INVENTION

The printing process and the development processing operations have beenshortened and speeded up with the photosensitive materials used forprints in recent years, and increasingly strong demands have arisen forhigher speeds, increased processing stability and increased strength forhandling purposes.

The most basic way of increasing the speed of a silver halide emulsionis to increase the grain size and thereby increase the amount of lightwhich is adsorbed per grain. In the case of a dye sensitized emulsion,this is done in such a way that the light is absorbed by the dye suchthat the photoelectrons are transmitted to the silver halide and thereis a link with the latent image formation. However, these methods do notalways give satisfactory results, and increasing grain size impedes anyspeeding up of the development process. Also with dye sensitization, notonly is development and desilvering impeded but, under normalconditions, there is little latitude for increasing speed by increasingthe amount of dye sensitizing agent etc. Hence, the ability to increasethe speed of silver halide grains without increasing the size of thegrains and without increasing the amount of sensitizing dye would bevery useful. The methods known as chemical sensitization methods aretypical of the methods which are used for this purpose, and the knownmethods include those in which sulfur sensitizing agents such as sodiumthiosulfate are used, those in which gold sensitizers such as potassiumchloroaurate are used, those in which reduction sensitizing agents suchas stannous chloride are used, and those in which these types ofsensitization are used jointly. The speed which can be attained withthese various methods of chemical sensitization is governed by the typeof sensitizing agent and the amount which is added, and by the methodused for making the addition and the composition, but the details havenot yet been clarified, and it is known that different results ariseaccording to the nature of the silver halide grains themselves prior tochemical sensitization. For example, it has been disclosed in "TheJournal of Photographic Science", 14, 181 (1966) that differences arisewith sulfur sensitization depending on the crystal habit of the silverhalide grains, but it is noted on pages 249 to 256 of volume 23 (1975)of the same journal that the crystal habit of the grains, includingreduction sensitization, may fulfill some role in latent imageformation. Furthermore, the types of halogen from which the emulsiongrains are formed, crystal habit, and the effect on the speed andfogging of sulfur sensitization and gold/sulfur sensitization on thesematerials have been discussed in "Photographic Science and Engineering"28, 146 (1984). However, these reports only describe the effect of thenature of the silver halide emulsion grains on chemical sensitizationand photographic speed and they give no indication of techniques ormethods for responding to the demands for higher speeds and handlingstability at the commercial level of the type referred to earlier.

Methods of realizing an effective increase in speed without increasingthe silver halide grain size have been anticipated in the silver halidephotographic materials as described above. When speed is increased inthis way then further improvements in stability in processing androbustness in handling can also be anticipated.

The method of forming grains by so-called halogen exchange disclosed inJP-B-No. 50-36978 is one known method of increasing the sensitivity ofsilver halides. (The term "JP-B" as used herein means an examinedJapanese patent publication.)

The silver halide emulsions formed using this method are characterizedby having a higher speed and by having a reduced tendency to fogging asa result of the application of mechanical pressure. However, while theemulsions do have these distinguishing features, the inventors havediscovered that they are accompanied by serious disadvantages. Thus, notonly is the tendency towards fogging on the application of mechanicalpressure reduced, but when parts to which pressure has been applied areexposed to light there is a marked loss of sensitivity. The extent ofhalogen exchange can be reduced in order to minimize thisdesensitization due to pressure, but in such cases fogging is liable toresult from the application of pressure. Thus, there is a problem withboth fogging and desensitization due to pressure and the two areincompatible. Moreover, it has been discovered that gradation issoftened in halogen exchanged emulsions in which the extent of halogenexchange has been reduced.

Furthermore, the inventors have previously disclosed emulsions for whichhalogen exchange has been carried with mono-disperse emulsions usingwater soluble bromides in the presence of a cyanine dye, and whencompared to the emulsions disclosed in JP-B-No. 50-36978, the emulsionsobtained in this way were better in that they were excellent in respectof high speed, pressure desensitization and pressure fogging, but thedevelopment of a further technique was required to achieve more perfectpressure characteristics and high speed and high contrast.

Hence, this invention represents progress in this direction and it isintended to provide stable silver halide emulsions which have high speedand high contrast. In more practical terms, the invention is intended toprovide a method for the manufacture of silver halide emulsions which,when chemically sensitized, have a high speed and high contrast andwhich have excellent pressure characteristics, and to provide silverhalide photographic materials which contain these emulsions.

SUMMARY OF THE INVENTION

The object of the invention has been realized by means of a silverhalide photographic material wherein an essentially silver iodide freesilver chloride, silver bromide or silver chlorobromide emulsionobtained: (1) by recrystallization of from 0.3 to 15 mol % of totalsilver halide using fine crystals of a sparingly soluble bromide,chloride or chlorobromide under conditions in which at least one of asimple cyanine dye, carbocyanine dye or dicarbocyanine dye is present onthe surface of the silver halide grains in a silver halide emulsionwhich has a grain size distribution such that the variation coefficientis not more than 0.25, and (2) by chemical sensitization, is present inat least one emulsion layer on a support.

DETAILED DESCRIPTION OF THE INVENTION

The sparingly soluble bromides, chlorides or chlorobromides are metalcompounds which are not liable to release bromide ions or chloride ionsin aqueous solution, and those used in this invention are compounds ofwhich the solubility is not more than 1 gram in 100 grams of water at20° C. Those which have a solubility of not more than 0.2 gram in 100grams of water at 20° C. are preferred. They include, for example, aniridium salt, a gold salt, a mercury salt, a thallium salt, a coppersalt, a lead salt, a platinum salt, a palladium salt, and a rhodiumsalt. Actual examples include silver bromide, irridium monobromide,irridium dibromide, irridium tribromide, aurous bromide, mercurousbromide, mercuric bromide, thallous bromide, cuprous bromide, leadbromide, niobium tribromide, platinous bromide, platinic bromide,palladous bromide, boron tribromide, molybdenum dibromide, molybdenumtribromide, anhydrous rhodium tribromide or co-salts or complex saltswhich contain two or more of these bromides, or mixtures of thesebromides, and the corresponding compounds for chlorides andchlorobromides. The addition of mixtures of these compounds ispreferred. In cases where mixed crystals (e.g., with silver salt) areformed, the mixed crystal itself should be sparingly soluble but themixed crystals may be formed from a sparingly soluble salt and a readilysoluble salt.

For example, silver bromide and readily soluble irridium salts formmixed crystals and these should be sparingly soluble.

In this invention the recrystallization must be achieved by the additionof sparingly soluble bromide, chloride or chlorobromide fine crystalsand so the silver halide grains prior to recrystallization preferablycontain a silver salt of a different halogen composition or they have adifferent grain size so that a sparingly soluble silver salt can beformed by recrystallization. The silver chloride content of the emulsionprior to recrystallization can have any value from 0 mol % to 100 mol %,but a silver chloride content of at least 4 mol % is desirable. Theamount of the sparingly soluble bromide, chloride or chlorobromide whichis added cannot be less than the amount of silver salt which is to berecrystallized, but it may be more than this amount. The amount addedmust be within the range of from 0.3 mol % to 15 mol % with respect tototal silver halide. Preferably, the amount added is within the rangefrom 0.6 mol % to 12 mol %, more preferably from 0.6 mol % to 9 mol %,and most preferably from 0.6 mol % to 6 mol %. Thus, the effect of theaddition is difficult to discern if the amount added is less than 0.3mol % while the addition of more than 15 mol % results in a markedincrease in the desensitization due to pressure mentioned earlier andthis does not provide the desired result. No particular limits are setfor the temperature of the emulsion during halogen exchange orrecrystallization, but a temperature of not more than 70° C. ispreferred. Most desirably, the temperature is not more than 60° C.

In the preferred embodiments of the present invention, there are caseswhere (a) the fine crystal is a sparingly soluble chlorobromide and thesurface of the silver halide grain which is subjected torecrystallization is a silver chlorobromide, (b) the fine crystal is asparingly soluble chlorobromide and the surface of the silver halidegrain which is subjected to recrystallization is a silver chloride, (c)the fine crystal is a sparingly soluble bromide and the surface of thesilver halide grain which is subjected to recrystallization is a silverchlorobromide, and (d) the fine crystal is a sparingly soluble chlorideand the surface of the silver halide grain is a silver chloride or asilver chlorobromide. Furthermore, there is a case where the differencebetween the silver bromide content of the silver halide grain which issubjected to recrystallization and the bromide content of the sparinglysoluble fine crystal is at least 10 mol %.

The recrystallization in this invention is carried out in the presenceof simple cyanine dyes, carbocyanine dyes or dicarbocyanine dyes.

These cyanine dyes can be represented by the general formula [I] below(the position of the double bonds moves according to the resonancestructure): ##STR1## In this formula, L represents a methine group or asubstituted methine group, R₁ and R₂ each represent an alkyl group or asubstituted alkyl group, Z₁ and Z₂ each represent a group of atoms whichforms a nitrogen containing five or six membered heterocyclic nucleus, Xrepresents an anion, n represents 1, 3 or 5, n₁ and n₂ each represent 1or 2 (n₁ =n₂ =0 when n=5, and n₁ or n₂ =0 when n=3), and m represents 0or 1 (0 when an intramolecular salt is formed). Furthermore, when n is 5the L groups may be joined together to form a substituted orunsubstituted five or six membered ring.

The cyanine dyes which can be represented by the general formula [I] aredescribed in detail below.

The substituent groups for the substituted methine groups represented byL are lower alkyl groups (for example, methyl, ethyl) and aralkyl groups(for example, benzyl, phenethyl), etc.

The alkyl groups (residual groups) represented by R₁ and R₂ may belinear chain, branched chain or cyclic alkyl groups. No particular limitis set for the number of carbon atoms, but it is preferably from 1 to 8,and more preferably from 1 to 4. Examples of substituent groups for thealkyl groups include sulfonic acid groups, carboxylic acid groups,hydroxyl groups, alkoxyl groups, acyloxy groups and aryl groups (forexample, phenyl) and these groups may be bonded to the alkyl groupsindividually or in combinations of two or more groups. Furthermore, thesulfonic acid groups and the carboxylic acid groups can form salts withalkali metal ions or quaternary ions of organic amines etc. Here, theterm "combinations of two or more groups" includes cases in which thegroups are each bonded individually to the alkyl group and cases inwhich the groups are linked together and bonded to the alkyl group.Examples of the latter case include sulfoalkoxyalkyl groups,sulfoalkoxyalkoxyalkyl groups, carboxyalkoxyalkyl groups, andsulfophenylalkyl groups.

A methyl group, ethyl group, n-propyl group, butyl group, pentyl group,vinylmethyl group, 2-hydroxyethyl group, 4-hydroxybutyl group,2-acetoxyethyl group, 3-acetoxypropyl group, 2-methoxyethyl group,4-methoxybutyl group, 2-carboxyethyl group, 3-carboxypropyl group,2-(2-carboxyethoxy)ethyl group, 2-sulfoethyl group, 3-sulfopropyl group,3-sulfobutyl group, 4-sulfobutyl group, sulfopentyl group,2-hydroxy-3-sulfopropyl group, 2-(3-sulfopropoxy)ethyl group,2-acetoxy-3-sulfopropyl group, 3-methoxy-2-(3-sulfopropoxy)propyl group,2-[2-(sulfopropoxy)ethoxy]ethyl group,2-hydroxy-3-(3'-sulfopropoxy)propyl group, etc. are typical examples ofthe groups represented by R₁ and R₂.

The preferred R₁ and R₂ include an ethyl, n-propyl, butyl, pentyl,sulfoethyl, sulfopropyl, sulfobutyl, and sulfopentyl group.

Typical examples of the nitrogen containing heterocyclic nuclei formedby Z₁ or Z₂ include oxazole nucleus, thiazole nucleus, selenazolenucleus, imidazole nucleus, pyridine nucleus, oxazoline nucleus,thiazoline nucleus, selenazoline nucleus, imidazoline nucleus and thosenuclei in which these nuclei are condensed with a benzene ring,naphthalene ring or other saturated or unsaturated carbocyclic ring, andsubstituent groups (for example, alkyl, trifluoromethyl, alkoxycarbonyl,cyano, carboxylic acid, carbamoyl, alkoxy, halogen atoms, aryl, acyl,hydroxyl), can be bonded onto these heterocyclic rings as substituentgroups.

The preferred Z₁ and Z₂ include a substituted benzoxazole nucleus, asubstituted benzothiazole nucleus, and a substituted benzoselenazolenucleus.

Cl-, Br-, I-, SO₄ ²⁻, NO₃ ⁻, ClO₄ ⁻, p-toluenesulfonic acid anion, etc.can be cited as anions which can be represented by X.

The preferred X includes Br-, I-, and p-toluenesulfonic acid anion.

Actual examples of cyanine dyes which can be represented by the generalformula [I] are listed below. ##STR2##

Those of these dyes which contain a benzothiazole nucleus or abenzoxazole nucleus are especially desirable.

Normally, methods in which the spectrally sensitizing dye is adsorbed onthe surface of the grains after the silver halide grains have beenformed completely are used to sensitize a silver halide emulsionspectrally. On the other hand, the possibility of reducing the amount ofdye which is not adsorbed by adding a merocyanine dye during theprecipitation and formation of the silver halide grains is disclosed inU.S. Pat. No. 2,735,766. Furthermore, a method in which spectrallysensitizing dye is added and adsorbed during the addition of the aqueoussilver salt solution and the aqueous halide solution with which thesilver halide grains are being formed was disclosed in JP-A-No. 55-26589(the term "JP-A" as used herein signifies a published, unexamined,Japanese patent application). With both of these methods the spectrallysensitizing dye is introduced during the formation of the silver halidegrains, which is to say at the stage where silver ions are being addedin the presence of silver halide grains, and adsorption is strengthenedin this way while the significance of this is lost with addition aftergrain formation has been completed.

In this invention, the cyanine dye may be added at any stage providedthat it is adsorbed and present on the surface of the silver halidegrains which have been formed at the stage where the recrystallizationby means of a sparingly soluble bromide, chloride or chloro bromide iscarried out. Hence, if the recrystallization is carried out immediatelyafter grain formation the cyanine dye is preferably added during grainformation, but in cases where the recrystallization is carried out sometime after grain formation the cyanine dye can be added after grainformation. Moreover, the addition of the cyanine dyes can be madesequentially with, simultaneously with, or after the addition of thesparingly soluble bromide, chloride or chlorobromide which is used forrecrystallization provided that the addition is made before thecompletion of recrystallization. In such a case, the good methods arethose in which the temperature of the system is kept low until thecyanine dye is added. The addition of the cyanine dye and the sparinglysoluble bromide, chloride or chlorobromide can be concentrated over ashort period of time or they can be added continuously over an extendedperiod of time. Furthermore, the addition times can be partiallyoverlapping. Furthermore, each substance added may be divided into twoor more portions and added in parts, or materials which have beendivided up in this way may be added alternately. The addition of thecyanine dye can be made by dissolving the dye in water, but addition inthe form of a solution in a water soluble organic solvent such as analcohol which has from 1 to 3 carbon atoms, or acetone, or in the formof a liquid obtained by means of a micellar dispersion with asurfactant, is preferred.

The amount of cyanine dye added is dictated by the type of spectralsensitization required, but in general it is determined by the amount ofsilver salt which is to be recrystallized and the recrystallizationconditions. Normally it is added at a rate of from 1×10⁻⁵ to 1×10⁻² mol,and preferably at a rate of from 3×10⁻⁵ to 5×10⁻³ mol, per mol silverhalide in total.

The sparingly soluble bromides, chlorides or chlorobromides may be addedin any form in this invention. Thus, they may be added to the system inthe form of a powder or they can be added in the form of a dispersion.

The use of sparingly soluble bromides, chlorides of chlorobromide whichhave been formed by precipitation in a protective colloid such asgelatin for example using readily soluble metal salts and bromides,chlorides or chlorobromides which are readily soluble in water ispreferred. The addition of sparingly soluble salts other than silversalts in the form of a gelatin dispersion in which mixed crystals with asilver salt have been formed is especially desirable.

In this invention, the emulsion which is to be subjected to halogenexchange in the presence of a cyanine dye must be an essentially silveriodide free silver chloride, silver bromide or silver chlorobromideemulsion which has a grain size distribution such that the variationcoefficient is not more than 0.25%. The extent of the recrystallizationvaries between grains if the variation coefficient is larger than thislevel and the desired effect cannot be achieved. The variationcoefficient is preferably not more than 0.2, more preferably it is notmore than 0.15 and most preferably, it is not more than 0.10. Thevariation coefficient is explained in T. H. James, The Theory of ThePhotographic Process, 3rd ed. page 39 (1967). The silver halideemulsions used in the invention contain essentially no silver iodide atall or not more than 3 mol % of silver iodide. The emulsion grains priorto recrystallization which are used in the invention may have a uniformhalogen composition throughout the whole of the grain, the halogencomposition in the interior and surface layer may be different, or theymay have a junction structure or a multi-phase structure. Furthermoremixtures of these types can be used. For example, silver chlorobromidegrains which have different phases may be grains which have a nucleus orone or a plurality of layers within the grains which are richer insilver bromide than the average halogen composition. Conversely, theymay be grains which have a nucleus or layers which are richer in silverchloride than the average halogen composition. In either case, thegrains after recrystallization are silver halide grains of which atleast part of the surface layer has a different chemical composition tothe interior or other parts of the surface layer.

The average grain size of the silver halide (the average diameter ofcircles calculated on the basis of projected areas) is not more than2.2μ but at least 0.1μ, and preferably not more than 1.2μ but at least0.2.

Two or more silver halide emulsions of this invention of different grainsize can be coated together in the same layer or lamination coated inseparate layers as emulsion layers which have essentially the same colorsensitivity in order to satisfy the gradation which is required of thephotosensitive material. Mixtures and laminates with silver halideemulsions outside the scope of this invention can also be used.

The silver halide grains used in the invention preferably have a regularcrystalline form, such as a cubic, octahedral, dodecahedral,tetradecahedral form etc., but grains which have an irregularcrystalline form, such as a spherical form, and grains which have acomplex crystalline form in which these forms are combined can also beused provided that the variation coefficient of the grain sizedistribution is not more than 0.25. The grains may be tabular grains,and emulsions in which tabular grains of which the value of thelength/thickness ratio is at least 5, and preferably at least 8, accountfor at least 50% of the projected area of all the grains can be used inparticular. The form of the grains after recrystallization differssomewhat from the original form but this difference is of noconsequence. The emulsion grains which have been formed are preferablyof the surface latent image type with which the latent image is formedprincipally on the surface of the grains.

The photographic emulsions which are used in the invention can beprepared using the method described in Chemie et PhysiquePhotographique, by P. Glafkides, published by Paul Montel, 1967; inPhotographic Emulsion Chemistry, by G. F. Duffin, published by FocalPress, 1966; and in Making and Coating Photographic Emulsions, by V. L,Zelikman et al., published by Focal Press, 1964 etc. That is to say,they can be prepared using the acid method, the neutral or the ammoniamethod and a one sided mixing method, a simultaneous mixing method or acombination of these methods can be used for the system by which asoluble silver salt is reacted with a soluble halide. Methods in whichthe grains are formed in the presence of an excess of silver ion (theso-called reverse mixing methods) can also be used. The method in whichthe pAg value of the liquid phase in which the silver halide is beingformed is held constant, which is to say the controlled double jetmethod, can be used as one type of simultaneous mixing method. Silverhalide emulsions of which the crystal form is regular and in which thegrains are almost uniform can be obtained using this method.

The additives which can be used when preparing silver halide grains bymeans of this invention are described below.

Thus silver halide solvents such as, for example, ammonia, potassiumthiocyanate, ammonium thiocyanate, thioether compounds (for examplethose disclosed in U.S. Pat. Nos. 3,271,157, 3,574,628, 3,704,130,4,297,439 and 4,276,374 etc.), thione compounds (for example thosedisclosed in JP-A-No. 53-144319, JP-A-No. 53-82408 and JP-A-No. 55-77737etc.) and amine compounds (for example those disclosed in JP-A-No.54-100717 etc.) etc. can be used to control grain growth during theformation of silver halide grains in accordance with this invention.

Cadmium salts, zinc salts, thallium salts, irridium salts or complexsalts thereof, rhodium salts or complex salts thereof, or iron salts orcomplex salts thereof may also be present during the course of theformation or physical ripening of the silver halide grains.

Sulfur sensitization can be carried out in accordance with the normalmethods used for sulfur sensitization. That is to say, compounds whichcontain sulfur which can react with silver halide, for examplethiosulfates, thioureas, mercapto compounds, rhodanines etc. can be usedfor this purpose. Details of the sulfur sensitization method have beendisclosed in the specifications of U.S. Pat. Nos. 2,410,689 and3,501,313, in West German Pat. No. 1,422,869, and in JP-B-No. 49-20533.

The sulfur sensitizing agent is preferably used at a rate within therange of from about 10⁻⁸ to 5×10⁻⁴ mol per mol of silver halide.

Furthermore, other methods of sensitization can be used conjointly withsulfur sensitization.

That is to say, the reduction sensitization method in which reducingsubstances (for example stannous salts, amines, hydrazine derivatives,formamidinesulfinic acid, silane compounds) are used, and precious metalsensitization methods in which precious metal compounds (for examplegold salts, or complex salts of metals of group VIII of the periodictable, such as platinum, irridium, lead etc.) are used, can be used forthis purpose.

Reduction sensitization methods and precious metal sensitization methodshave been disclosed in U.S. Pat. Nos. 2,399,083, 2,597,856, 2,597,915,2,487,850 and 2,518,698, etc.

Various compounds can be included in the photographic emulsions whichare used in the invention with a view to preventing the occurrence offogging during the manufacture, storage or photographic processing ofthe photosensitive materials or with a view to stabilizing photographicperformance. Thus many compounds which are known as anti-fogging agentsor stabilizers, such as azoles, for example benzothiazolium salts,nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especiallythe nitro and halogen substituted benzimidazoles); heterocyclic mercaptocompounds, for example mercaptothiazoles, mercaptobenzothiazoles,mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles,mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole),mercaptopyrimidines; heterocyclic mercapto compounds as indicated abovewhich have water solubilizing groups such as carboxyl groups and sulfogroups, thioketone compounds, for example oxazolinethione; azaindenes,for example tetraazaindenes (especially 4-hydroxy substituted(1,3,3a,7)tetraazaindenes); benzenethiosulfonic acids andbenzenesulfinic acids etc. can be added for this purpose.

Yellow couplers, magenta couplers and cyan couplers which couple withthe oxidized form of a primary aromatic amine developing agent and forma yellow, magenta or cyan coloration respectively are normally used incases where the photosensitive materials of this invention are used ascolor sensitive materials.

Of the yellow couplers which can be used in this invention, the use ofthe acylacetamide derivatives, such as the benzoylacetanilides andpivaloylacetanilides etc., is preferred.

Those of these compounds which can be represented by the generalformulae [Y-1] and [Y-2] indicated below are ideal as yellow couplers.##STR3## In these formulae, X₁ represents a hydrogen atom or a couplingleaving group. R₂₁ represents a group which renders the molecule fast todiffusion which has a total number of from 8 to 32 carbon atoms, and R₂₂represents a hydrogen atom, one or more halogen atoms, lower alkylgroups, or groups which render the molecule fast to diffusion which havea total number of from 8 to 32 carbon atoms. R₂₃ represents a hydrogenatom or substituent groups. In cases where there are two or more groupsrepresented by R₂₃ these groups may be the same or different.

Details of pivaloylacetanilide type yellow couplers are given from line15 of column 3 to line 39 of column 8 of the specification of U.S. Pat.No. 4,622,287 and from line 50 of column 14 to line 41 of column 19 ofthe specification of U.S. Pat. No. 4,623,616.

Details of benzoylacetanilide type yellow couplers have been disclosedin U.S. Pat. Nos. 3,408,194, 3,933,501, 4,046,575, 4,133,958 and4,401,752 etc.

Typical examples of pivaloylacetanilide type yellow couplers include thecompounds (Y-1) to (Y-39) disclosed in columns 37 to 54 of thespecification of the aforementioned U.S. Pat. No. 4,622,287, and ofthese compounds the use of (Y-1), (Y-4), (Y-6), (Y-7), (Y-15), (Y-21),(Y-22), (Y-23), (Y-26), (Y-35), (Y-36), (Y-37), (Y-38) and (Y-39) ispreferred.

The illustrative compounds (Y-1) to (Y-33) are given between column 19and column 24 of the specification of the aforementioned U.S. Pat. No.4,623,616, and of these compounds, those indicated as (Y-2), (Y-7),(Y-8), (Y-12), (Y-20), (Y-21), (Y-23) and (Y-29) are preferred.

Other preferred yellow couplers include typical example (34) noted incolumn 6 of the specification of U.S. Pat. No. 3,408,194, illustrativecompounds (16) and (19) disclosed in column 8 of the specification ofU.S. Pat. No. 3,933,501, illustrative compound (9) disclosed in columns7 to 8 of the specification of U.S. Pat. No. 4,046,575, illustrativecompound (1) disclosed in columns 5 to 6 of the specification of U.S.Pat. No. 4,133,958, illustrative compound 1 disclosed in column 5 of thespecification of U.S. Pat. No. 4,401,752, and the compounds (a) to (g)set forth below.

    __________________________________________________________________________     ##STR4##                                                                     Compound                                                                            R.sub.22            X.sub.1                                             __________________________________________________________________________           ##STR5##                                                                                          ##STR6##                                           b                                                                                    ##STR7##           "                                                   c                                                                                    ##STR8##                                                                                          ##STR9##                                           d     "                                                                                                  ##STR10##                                          e     "                                                                                                  ##STR11##                                          f     NHSO.sub.2 C.sub.12 H.sub.25                                                                       ##STR12##                                          g     NHSO.sub.2 C.sub.16 H.sub.33                                                                       ##STR13##                                          __________________________________________________________________________

Those of the couplers described above in which the leaving atom is anitrogen atom are especially desirable.

Furthermore, the oil protected type indazole based or cyanoacetyl basedcouplers, and preferably the 5-pyrazolone based couplers and thepyrazoloazole based couplers, such as the pyrazoloazoles, can be used asthe magenta couplers which are used in the invention. The 5-pyrazolonebased couplers which are substituted with an arylamino group or anacylamino group in the 3-position are preferred from the point of viewof the hue of the colored dye and color forming density, and typicalexamples have been disclosed in U.S. Pat. Nos. 2,311,082, 2,343,703,2,600,788, 2,908,573, 3,062,653, 3,152,896 and 3,936,015 etc. Thenitrogen atom leaving groups disclosed in U.S. Pat. No. 4,310,691 andthe arylthio groups disclosed in U.S. Pat. No. 4,351,897 are preferredas the leaving groups of two equivalent 5 pyrazolone based couplers.Furthermore, high color densities can be obtained with the 5-pyrazolonebased couplers which have ballast groups disclosed in European Pat. No.73,636.

The pyrazolobenzimidazoles disclosed in U.S. Pat. No. 3,369,879, andpreferably the pyrazolo[5,1-c][1,2,4]triazoles disclosed in U.S. Pat.No. 3,725,067, the pyrazolotetrazoles disclosed in Research Disclosure24220 (June 1984) and the pyrazolopyrazoles disclosed in ResearchDisclosure 24230 (June 1984) can be used as pyrazoloazole basedcouplers. All of the couplers mentioned above may take the form ofpolymeric couplers.

In practice, these compounds can be represented by the general formulae[M-1], [M-2] or [M-3] which are set forth below. ##STR14## In theseformulae R₃₁ represents a group which is fast to diffusion which has atotal number of from 8 to 32 carbon atoms, and R₃₂ represents a phenylgroup or a substituted phenyl group. R₃₃ represents a hydrogen atom or asubstituent group. Z represents a group of nonmetal atoms required toform a five membered azole ring which has a nitrogen atoms in the 2 to 4positions, and the azole ring may have substituent groups (includingcondensed rings). X₂ represents a hydrogen atom or a leaving group.Details of the substituent groups for R₃₃ and of the substituent groupsfor the azole ring have been disclosed, for example, from line 41 ofcolumn 2 to line 27 of column 8 of the specification of U.S. Pat. No.4,540,654.

From among the pyrazoloazole based couplers the use of theimidazo[1,2-b]pyrazoles disclosed in U.S. Pat. No. 4,500,630 ispreferred in view of the low absorption by the colored dye on the yellowside absorption and light fastness, and the use of thepyrazolo[1,5-b][1,2,4]triazoles disclosed in U.S. Pat. No. 4,540,654 isespecially desirable.

Moreover, the use of the pyrazolotriazole couplers which have a branchedalkyl group bonded directly to the 2-, 3- or 6-position of thepyrazolotriazole ring as disclosed in JP-A-No. 61-65245, thepyrazoloazole couplers which contain a sulfonamido group within themolecule as disclosed in JP-A-No. 61-65246, the pyrazoloazole couplerswhich have an alkoxyphenylsulfonamido ballast group as disclosed inJP-A-No. 61-147254, and the pyrazolotriazole couplers which have analkoxy group or aryloxy group in the 6-position as disclosed in EP-A-No.226849 is preferred.

Actual examples of these couplers are set forth below.

    __________________________________________________________________________     ##STR15##                                                                    Com-                                                                          pound                                                                             R.sub.33               R.sub.34                X.sub.2                    __________________________________________________________________________    M-1 CH.sub.3                                                                                              ##STR16##              Cl                         M-2 "                                                                                                     ##STR17##              "                          M-3 "                                                                                                     ##STR18##                                                                                             ##STR19##                 M-4                                                                                ##STR20##                                                                                            ##STR21##                                                                                             ##STR22##                 M-5 CH.sub.3                                                                                              ##STR23##              Cl                         M-6 "                                                                                                     ##STR24##              "                          M-7                                                                                ##STR25##                                                                                            ##STR26##                                                                                             ##STR27##                 M-8 CH.sub.3 CH.sub.2 O    "                       "                          M-9                                                                                ##STR28##                                                                                            ##STR29##              "                          M-10                                                                               ##STR30##                                                                                            ##STR31##              Cl                         __________________________________________________________________________

    __________________________________________________________________________     ##STR32##                                                                    Compound                                                                            R.sub.33         R.sub.34                     X.sub.2                   __________________________________________________________________________    M-11  CH.sub.3                                                                                        ##STR33##                   Cl                        M-12  "                                                                                               ##STR34##                   "                         M-13                                                                                 ##STR35##                                                                                      ##STR36##                   "                         M-14                                                                                 ##STR37##                                                                                      ##STR38##                   "                         M-15                                                                                 ##STR39##                                                                                      ##STR40##                   Cl                        M-16                                                                                 ##STR41##                                                                                      ##STR42##                                                                                                  ##STR43##                __________________________________________________________________________

The phenol based cyan couplers and the naphthol based couplers are themost typical cyan couplers.

There are the phenol based cyan couplers (including polymer couplers)which have an alkyl group in the 5-position and an acylamino group inthe 2-position of the phenol ring as disclosed in U.S. Pat. Nos.2,369,929, 4,518,687, 4,511,647 and 3,772,002 etc., and typical examplesinclude the coupler of illustrative example 2 described in Canadian Pat.No. 625,822, compound (1) described in U.S. Pat. No. 3,772,002,compounds (I-4) and (I-5) described in U.S. Pat. No. 4,564,590,compounds (1), (2), (3) and (24) described in JP-A-No. 61-39045 andcompound (C-2) described in JP-A-No. 62-70846.

There are also the 2,5-diacylaminophenol based couplers disclosed asphenol based cyan couplers in U.S. Pat. Nos. 2,772,162, 2,895,826,4,334,011 and 4,500,653 and in JP-A-No. 59-164555, and typical examplesof these include compound (V) described in U.S. Pat. No. 2,895,826,compound (17) described in U.S. Pat. No. 4,557,999, compounds (2) and(12) described in U.S. Pat. No. 4,565,777, compound (4) described inU.S. Pat. No. 4,124,396, and compound (I-19) described in U.S. Pat. No.4,613,564, etc.

Furthermore there are the phenol based cyan couplers in which a nitrogencontaining heterocyclic ring is condensed with the phenol ring asdisclosed in U.S. Pat. Nos. 4,327,173, 4,564,586 and 4,430,423, inJP-A-61-390441 and in JP-A-No. 62-257158, and typical examples of thesecyan couplers included the couplers (1) and (3) described in U.S. Pat.No. 4,327,173, compounds (3) and (16) described in U.S. Pat. No.4,564,586, compounds (1) and (3) described in U.S. Pat. No. 4,430,423,and the compounds set forth below. ##STR44##

There are also ureido based couplers disclosed in U.S. Pat. Nos.4,333,999, 4,451,559, 4,444,872, 4,427,767 and 4,579,813 and in EuropeanPatent (EP) No. 067,689B1 etc as phenol based cyan couplers, and typicalexamples of these include the coupler (7) described in U.S. Pat. No.4,333,999, coupler (1) described in U.S. Pat. No. 4,451,559, coupler(14) described in U.S. Pat. No. 4,444,872, coupler (3) described in U.S.Pat. No. 4,427,767, couplers (6) and (24) described in U.S. Pat. No.4,609,619, couplers (1) and (11) described in U.S. Pat. No. 4,579,813,couplers (45) and (50) described in European Patent (EP) No. 067,689B1,and coupler (3) described in JP-A-No. 61-42658, etc.

There are also naphthol based cyan couplers which have anN-alkyl-N-arylcarbamoyl group in the 2 position of the naphthol ring(for example U.S. Pat. No. 2,313,586), which have an alkylcarbamoylgroup in the 2-position (for example U.S. Pat. Nos. 2,474,293 and4,282,312), which have an arylcarbamoyl group in the 2-position (forexample JP-B-No. 50-14523), and which have a carbonamido or sulfonamidogroup in the 5-position (for example JP-A-No. 60-237448, JP-A-No.61-145557 and JP-A-No. 61-153640), and naphthol based couplers whichhave an aryloxy leaving group (for example U.S. Pat. No. 3,476,563),which have a substituted alkoxy leaving group (for example U.S. Pat. No.4,296,199) and which have a glycolic acid leaving group (for exampleJP-B-No. 60-39217), etc.

The photosensitive material of this invention may contain hydroquinonederivatives, aminophenol derivatives, amines, gallic acid derivatives,catechol derivatives, ascorbic acid derivatives, colorless couplers,sulfonamidophenol derivatives etc. as anticolor fogging agents oranti-color mixing agents.

Various anti-color fading agents can also be used in the photosensitivematerials of this invention. That is to say, typical examples of organicanti-color fading agents which can be used for cyan, magenta and yellowimages include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans,spirochromans, p-alkoxyphenols, hindered phenols centered on thebisphenols, gallic acid derivatives, methylenedioxybenzenes,aminophenols, hindered amines and ether and ester derivatives in whichthe phenolic hydroxyl groups of these compounds have been silylated oralkylated. Furthermore, metal complexes typified by the(bissalicylaldoxymato)nickel complex and the(bis-N,N-dialkyldithiocarbamato)nickel complex can be used for thispurpose

Actual examples of organic anti-color fading agents have been disclosedin the specifications of the following patents:

Hydroquinones have been disclosed in U.S. Pat. Nos. 2,360290, 2,418,613,2,700,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944 and4,430,425, in British Patent No. 1,363,921 and in U.S. Pat. Nos.2,710,801 and 2,816,028 etc., 6-hydroxychromans, 5-hydroxycoumarans andspirochromans have been disclosed in U.S. Pat. Nos. 3,432,300,3,573,050, 3,574,627, 3,698,909 and 3,764,337 and in JP-A-52-152225etc., spiroindanes have been disclosed in U.S. Pat. No. 4,360,589,p-alkoxyphenols have been disclosed in U.S. Pat. No. 2,735,765, inBritish Patent No. 2,066,975, in JP-A-59-10539 and in JP-B-57-19764etc., hindered phenols have been disclosed in U.S. Pat. No. 3,700,455,in JP-A-52-72225, in U.S. Pat. No. 4,228,235 and in JP-B-52-6623, etc.,gallic acid derivatives, methylenedioxybenzenes and aminophenols havebeen disclosed in U.S. Pat. Nos. 3,457,079 and 4,332,886 and inJP-B-56-21144 respectively, hindered amines have been disclosed in U.S.Pat. Nos. 3,336,135 and 4,268,593, in British Patent Nos. 1,326,889,1,354,313 and 1,410,846, in JP-B-51-1420, and in JP-A-58-114036,JP-A-59-53846 and JP-A-59-78344, etc., ether and ester derivatives ofphenolic hydroxyl groups have been disclosed in U.S. Pat. Nos.4,155,765, 4,174,220, 4,254,216 and 4,264,720, in JP-A-54-145530,JP-A-55-6321, JP-A-58-105147 and JP-A-59-10539, in JP-B-57-37856, inU.S. Pat. No. 4,279,990, and in JP-B-53-3263 etc., and metal complexeshave been disclosed in U.S. Pat. Nos. 4,050,938 and 4,241,155 and inBritish Patent No. 2,027,731(A) etc. These compounds can be used toachieve the intended purpose by coemulsification with the couplers andaddition to the photosensitive layer, normally at a rate of from 5 to100 wt % with respect to the corresponding coupler. The introduction ofultraviolet absorbers into layers on either side adjacent to the cyancolor forming layer is more effective for preventing deterioration ofthe cyan dye image by heat or, more especially, by light.

The use of the spiroindanes and hindered amines from among the abovementioned anti-color fading agents is especially desirable.

Ultraviolet absorbers can be included in the hydrophilic colloid layersof the photosensitive materials of this invention. For example, use canbe made of the benzotriazole compounds substituted with aryl groups (forexample those disclosed in U.S. Pat. No. 3,533,794), 4-thiazolidonecompounds (for example those disclosed in U.S. Pat. Nos. 3,314,794 and3,352,681), benzophenone compounds (for example those disclosed inJP-A-46-2784), cinnamic acid ester compounds (for example thosedisclosed in U.S. Pat. Nos. 3,705,805 and 3,707,375), butadienecompounds (for example those disclosed in U.S. Pat. No. 4,045,229), andbenzooxidol compounds (for example those disclosed in U.S. Pat. No.3,700,455). Ultraviolet absorbing couplers (for example the α-naphtholbased cyan dye forming couplers) or ultraviolet absorbing polymers canalso be used for this purpose. These ultraviolet absorbers may bemordanted into a specified layer.

Water soluble dyes can be included in the hydrophilic colloid layers ofthe photosensitive materials of this invention as filter dyes or foranti-irradiation and various other purposes Dyes of this type includeoxonol dyes, hemi-oxonol dyes, styryl dyes, merocyanine dyes, cyaninedyes and azo dyes. Of these dyes, the oxonol dyes, hemi-oxonol dyes andmerocyanine dyes are useful. Details of useful oxonol dyes have beendescribed from line 16 of the upper left column on page 158 to page 163of the specification of JP-A-62-215272.

The use of gelatin is convenient as the binding agent or protectivecolloid in the emulsion layers of the photosensitive materials of thisinvention, but other hydrophilic colloids can be used eitherindependently or in conjunction with gelatin.

The gelatin used in the invention may be a lime treated gelatin, or anacid treated gelatin can be used. Details of the manufacture of gelatinhave been described by Arthur Wiese in "The Macromolecular Chemistry ofGelatin" (published by Academic Press, 1964).

The cellulose nitrate films, cellulose acetate films, cellulose acetatebutyrate films, cellulose acetate propionate films, polystyrene films,polyethyleneterephthalate films, polycarbonate films, laminates of thesefilms, thin glass films, paper etc. normally used in photographicmaterials can be used as the support which is used in this invention.Supports such as papers which have been coated or laminated with barytaor an α-olefin polymer, especially a polymer made from an α-olefin whichhas from 2 to 10 carbon atoms, for example polyethylene, polypropylene,ethylene/butene copolymer etc., vinyl chloride resins which containreflecting substances such as TiO₂, and plastic films of which theadhesion with other polymeric materials has been improved by surfaceroughening as described in JP-B-47-19068 provide good results.Furthermore, ultraviolet curable resins can be used for this purpose.

A transparent support or a non-transparent support can be selectedaccording to the intended purpose of the photosensitive material.Furthermore, the supports can be rendered colored and transparent by theaddition of dyes or pigments.

Apart from the original non-transparent supports such as paper,non-transparent supports also include those made by adding dyes ororganic pigments such as titanium oxide to a transparent film andplastic films which have been surface treated using methods such asthose described in JP-B-47-19068, etc. An undercoating layer is normallyestablished on the support. Preliminary surface treatments such ascorona discharge treatments, ultraviolet irradiation and flametreatments etc. can also be used with these supports in order to improveadhesion properties.

The color photosensitive materials which can be used for making colorphotographs of this invention may be any of the usual types of colorphotographic materials, for example color negative films, color papers,color reversal papers, color reversal films, color positive films etc.

Black and white development baths and/or color development baths can beused for the development processing of the photosensitive materials ofthis invention. A color development bath preferably consists of anaqueous alkaline solution which contains a primary aromatic amine basedcolor developing agent as the principal component. Aminophenol basedcompounds are also useful as color developing agents, but the use ofp-phenylenediamine based compounds is preferred. Typical examples ofthese compounds include 3-methyl-4-amino-N,,N-diethylaniline,3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline,3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and the sulfate,hydrochloride and p-toluenesulfonate salts of these compounds. Two ormore of these compounds can be used conjointly, depending on theintended purpose.

The color development baths generally contain pH buffers such as alkalimetal carbonates, borates or phosphates, and development inhibitors oranti-fogging agents such as bromides, iodides, benzimidazoles,benzothiazoles or mercapto compounds etc. They may also contain, asrequired, various preservatives such as hydroxylamine,diethylhydroxylamine, sulfites, hydrazines, phenylsemicarbazides,triethanolamine, catechol sulfonic acids,triethylenediamine(1,4diazabicyclo[2,2,2]octane) etc., organic solventssuch as ethylene glycol and diethylene glycol, development acceleratorssuch as benzyl alcohol, poly(ethylene glycol), quaternary ammonium saltsand amines, color forming couplers, competitive couplers, fogging agentssuch as sodium borohydride, auxiliary developing agents such as1-phenyl-3-pyrazolidone, viscosity imparting agents, and variouschelating agents as typified by the aminopolycarboxylic acids,aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylicacids, typical examples of which include ethylenediamine tetraaceticacid, nitrilo triacetic acid, diethylenetriamine penta-acetic acid,cyclohexanediamine tetra-acetic acid, hydroxyethylimino diacetic acid,1-hydroxyethylidene1,1-diphosphonic acid,nitrilo-N,N,N-trimethylenephosphonic acid,ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, ethylenediaminedi(o-hydroxyphenylacetic acid), and salts of these compounds.

Color development is carried out after a normal black and whitedevelopment in the case of reversal processing. The known black andwhite developing agents, for example dihydroxybenzenes such ashydroquinone etc., 3-pyrazolidones such as 1-phenyl-3-pyrazolidone etc.,and aminophenols such as N-methyl-p-aminophenol etc., can be usedindividually or in combinations for the black and white developmentbath.

The pH of these color developers and black and white developers isgenerally within the range of from 9 to 12. Furthermore, thereplenishment rate of the development bath depends on the colorphotographic material which is being processed, but it is generally lessthan 3 liters per square meter of photosensitive material and it ispossible, by reducing the bromide ion concentration in the replenisher,to use a replenishment rate of less than 500 ml per square meter ofphotosensitive material. Prevention of the loss of liquid byevaporation, and aerial oxidation, by minimizing the contact area withthe air in the processing tank is desirable in cases where thereplenishment rate is low. Furthermore, the replenishment rate can bereduced by using a means of suppressing the accumulation of bromide ionin the developer.

The photographic emulsion layers are subjected to a normal bleachingprocess after color development. The bleaching process may be carriedout at the same time as the fixing process (in a bleach-fix process) orit may be carried out as a separate process. Moreover, a bleach-fixprocess can be carried out after a bleaching process in order tospeed-up processing. Moreover processing can be carried out in twoconnected bleach-fix baths, a fixing process can be carried out beforecarrying out a bleach-fix process or a bleaching process can be carriedout after a bleach-fixing process, according to the intended purpose ofthe processing. Compounds of a multi-valent metal such as iron(III),cobalt(III), chromium(VI), copper(II) etc., peracids, quinones, nitrocompounds etc. can be used as bleaching agents. Typical bleaching agentsinclude ferricyanides; dichromates; organic complex salts of iron(III)or cobalt(III), for example complex salts with aminopolycarboxylic acidssuch as ethylenediamine tetraacetic acid, diethylenetriaminepenta-acetic acid, cyclohexanediamine tetra-acetic acid, methyliminodiacetic acid, 1,3-diaminopropane tetra-acetic acid, glycol etherdiamine tetra-acetic acid etc. or citric acid, tartaric acid, malic acidetc.; persulfates; bromates; permanganates and nitrobenzenes etc. Ofthese materials the use of the aminopolycarboxylic acid iron(III)complex salts, principally ethylenediamine tetra-acetic acid iron(III)complex salts, and persulfates is preferred from the points of view ofboth rapid processing and the prevention of environmental pollution.Moreover, the amino polycarboxylic acid iron(III) complex salts areespecially useful in both bleach baths and bleach-fix baths. The pH of ableach or bleach-fix bath in which aminopolycarboxylic acid iron(III)complex salts ar being used in normally from 5.5 to 8, but processingcan be carried out at lower pH values in order to speed-up processing.

Bleach accelerators can be used, as required, in the bleach baths,bleach-fix baths, or bleach or bleach-fix pre-baths. Actual examples ofuseful bleach accelerators have been disclosed in the followingspecifications: Thus there are the compounds which have a mercapto groupor a disulfide group disclosed in U.S. Pat. No. 3,893,858, West GermanPatent Nos. 1,290,812 and 2,059,988, in JP-A-53-32736, JP-A-53-57831,JP-A-5-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631,JP-A-53-104432, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, and inResearch Disclosure No. 17129 (July 1978) etc.; the thiazolidinederivatives disclosed in JP-A-50-140129; the thiourea derivativesdisclosed in JP-B-45-8506, JP-A-52-20832 and JP-A-53-32735, and in U.S.Pat. No. 3,706,561; the iodides disclosed in West German Patent No.1,127,715 and in JP-A-58-16235; the polyoxyethylene compounds disclosedin West German Patent Nos. 966,410 and 2,748,430; the polyaminecompounds disclosed in JP-B-45-8836; the other compounds disclosed inJP-A-49-42434, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727,JP-A-55-26506 and JP-A-58-163940; and bromide ions etc. Among thesecompounds, those which have a mercapto group or a disulfide group arepreferred in view of their large accelerating effect, and the use of thecompounds disclosed in U.S. Pat. No. 3,893,858, in West German PatentNo. 1,290,812 and in JP-A-53-95630 is especially desirable. Moreover,the use of the compounds disclosed in U.S. Pat. No. 4,552,834 is alsodesirable. These bleach accelerators may be added to the sensitivematerial. These bleach accelerators are especially effective whenbleach-fixing color photosensitive materials for camera purposes.

Thiosulfates, thiocyanates, thioether based compounds, thioureas andlarge quantities of iodides etc. can be used as fixing agents, butthiosulfates are generally used for this purpose, and ammoniumthiosulfate in particular can be used in the widest range ofapplications. Sulfites or bisulfites, or carbonylbisulfite additioncompounds, are the preferred preservatives for bleach-fix baths.

The silver halide color photographic materials of this invention aregenerally subjected to a water washing and/or stabilizing process afterthe desilvering process. The amount of water used in the water washingprocess can be fixed within a wide range according to the nature of thephotosensitive material (for example the materials, such as thecouplers, which are being used), the use, the wash water temperature,the number of washing tanks (the number of washing stages), thereplenishment system, i.e., whether a counter-flow or a sequential-flowsystem is used, and various other conditions. The relationship betweenthe amount of water used and the number of water washing tanks in amulti-stage counter-flow system can be obtained using the methodoutlined on pages 248 to 253 of Journal of the Society of Motion Pictureand Television Engineers, Volume 64 (May 1955).

The amount of wash water can be greatly reduced by using the multi-stagecounter-flow system noted in the aforementioned literature, but bacteriaproliferate due to the increased residence time of the water in thetanks and problems arise as a result of the sediments which are formedbecoming attached to the photosensitive material. The method in whichthe calcium ion and manganese ion concentrations are reduced asdisclosed in JP-A-62-288838 can be used very effectively to overcomeproblems of this sort in the processing of color photosensitivematerials of this invention. Furthermore, the isothiazolone compoundsand thiabendazoles disclosed in JP-A-57-8542 and the chlorine baseddisinfectants such as chlorinated sodium isocyanurate, andbenzotriazoles etc., and the disinfectants disclosed in "Chemistry ofBiocides and Fungicides" by Horiguchi, "Reduction of Microorganisms,Biocidal and Fungicidal Techniques", published by the Health and HygieneTechnical Society and in "A Dictionary of Biocides and Fungicides",published by the Japanese Biocide and Fungicide Society, can be used forthis purpose.

The pH value of the wash water used in the processing of thephotosensitive materials of the invention is within the range from 4 to9, and preferably within the range from 5 to 8. The wash watertemperature and the washing time can be set variously according to thenature of the photosensitive material and the application etc. but, ingeneral, washing conditions of from 20 seconds to 10 minutes at atemperature of from 15 to 45° C., and preferably of from 30 seconds to 5minutes at a temperature of from 25 to 40° C., are selected Moreover,the photosensitive materials of this invention can be processed directlyin a stabilizing bath instead of being subjected to a water wash asdescribed above. The known methods disclosed in JP-A-57-8543,JP-A-58-14834 and JP-A-60-220345 can all be used for this purpose.

Furthermore, there are cases in which a stabilization process is carriedout following the aforementioned water washing process and thestabilizing baths which contain formalin and surfactant which are usedas a final bath for camera color photosensitive materials are an exampleof such a process. Various chelating agents and fungicides etc. can beadded to these stabilizing baths.

The overflow which accompanies replenishment of the above mentioned washwater and/or stabilizer can be re-used in .other processes such as thedesilvering process etc.

A color developing agent may also be incorporated into the silver halidecolor photosensitive material of this invention in order to simplify andspeed-up processing. The incorporation of various color developing agentprecursors is preferred. For example, the indoaniline based compoundsdisclosed in U.S. Pat. No. 3,342,597, the Schiff's base type compoundsdisclosed in U.S. Pat. No. 3,342,599 and in Research Disclosure Nos.14850 and 15159, the aldol compounds disclosed in Research DisclosureNo. 13924, the metal salt complexes disclosed in U.S. Pat. No.3,719,492, and the urethane based compounds disclosed in JP-A-53-135628can be used for this purpose.

Various 1-phenyl-3-pyrazolidones can be incorporated, as required, intothe silver halide color photosensitive materials of this invention witha view to accelerating color development. Typical compounds of this typehave been disclosed in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438etc.

The various processing baths are used at a temperature of from 10° to50° C. in this invention. The standard temperature is normally from 33°to 38° C., but processing is accelerated and the processing time isshortened at higher temperatures and, conversely, increased picturequality and improved stability of the processing baths can be achievedat lower temperatures. Furthermore, processes using hydrogen peroxideintensification or cobalt intensification as disclosed in West GermanPatent No. 2,226,770 or U.S. Pat. No. 3,674,499 can be carried out inorder to economize on silver in the photosensitive material.

The present invention will now be described by reference to specificnon-limiting examples Unless otherwise indicated all percents, ratios,parts, etc. are by weight.

EXAMPLE 1

Lime treated gelatin (30 grams) was added to 1000 cc of distilled waterand, after dissolving at 40° C., 6.5 grams of sodium chloride was addedand the temperature was raised to 75° C. A solution obtained bydissolving 62.5 grams of silver nitrate in 750 cc of distilled water anda solution obtained by dissolving 30.6 grams of potassium bromide and6.5 grams of sodium chloride in 500 cc of distilled water were added to,and mixed with, the aforementioned solution over a period of 40 minuteswhile maintaining the temperature at 75° C. Next, a solution obtained bydissolving 62.5 grams of silver nitrate in 500 cc of distilled water anda solution obtained by dissolving 30.6 grams of potassium bromide and6.5 grams of sodium chloride in 300 cc of distilled water were added toand mixed with the resulting mixture over a period of 20 minutes whilemaintaining the temperature at 75° C.

A solution obtained by dissolving 4.4 grams of potassium bromide in 50cc of distilled water was added 10 minutes after the completion of theaddition described above and, after stirring for a further period of 10minutes, the mixture was desalted and washed, 6 mg of sodium thiosulfatewas added and the emulsion was ripened for 40 minutes at 60° C. Thisemulsion (cubic grains of average grain size 0.53 μ, variationcoefficient 0.12) was coated, after the addition of the aforementionedsensitizing dye D-29 (3×10⁻⁴ mol/mol of silver), onto a cellulosetriacetate base in such a way that the coated weight of silver was 2.3g/m2 and the coated weight of gelatin was 3.3 g/m2 to provide sample A₁.

An emulsion prepared in the same way except that the sensitizing dyeD-29 was added at the rate of 3×10⁻⁴ mol per mol of silver 3 minutesafter the completion of the addition of the silver nitrate and silverhalide on the second occasion when preparing-the emulsion used in theproduction of sample A₁ was coated onto a cellulose triacetate base inthe same quantities as for sample A₁ to provide sample B₁.

Emulsions prepared in the same way as before except that the amount ofpotassium bromide added 10 minutes after the addition of the silver saltand halogen salts on the second occasion when preparing the emulsion ofsample B₁ was changed from 4.4 grams to 0.2 gram, 0.6 gram, 10.6 gramsand 21.9 grams were coated in the same way as sample B₁ to providesamples C₁, D₁, E₁ and F₁.

Emulsions were then prepared by adding emulsions (gelatin content 50g/kg, silver bromide content 122 g/kg, average grain size 0.06 μ,variation coefficient 0.07) which contained an equimolar amount ofsilver bromide in place of the potassium bromide solution which wasadded after 10 minutes in the preparation of the emulsions used insamples A₁ to F₁, and these emulsions were used to prepare thecorresponding samples A₂ to F₂ in the same way as before.

The samples A₁ to F₁, and A₂ to F₂ were exposed for 0.5 second to whitelight of color temperature 5400° K through an optical wedge and then thesamples were developed for 10 minutes at 20° C. using the developmentbath indicated below. The photographic density was measured in each caseand the results obtained are shown in Table 1.

    ______________________________________                                        Development Bath                                                              ______________________________________                                        Ascorbic acid       10          g                                             p-N-Methylaminophenol                                                                             2.4         g                                             Sodium carbonate    10          g                                             Potassium bromide   1           g                                             Water               to make up to 1                                                                           l                                             ______________________________________                                    

                                      TABLE 1                                     __________________________________________________________________________        Potassium                                                                            Cyanine dye (during                                                    bromide                                                                              exchange)          Pressure De-                                                                         Pressure                                 Sample                                                                            (g) (mol %)                                                                          (mol/mol Ag)                                                                            Speed                                                                             Fogging                                                                            sensitization                                                                        Fogging                                                                            Remarks                             __________________________________________________________________________    A.sub.1                                                                           4.4                                                                              (5) --        100 0.02 91     0.42 Comparative Ex.                     B.sub.1                                                                           4.4                                                                              (5) D-29 (3 × 10.sup.-4)                                                              121 0.02 97     0.09 Comparative Ex.                     C.sub.1                                                                           0.2                                                                              (0.2)                                                                             "          80 0.02 100    0.56 Comparative Ex.                     D.sub.1                                                                           0.6                                                                              (0.7)                                                                             "         103 0.02 97     0.18 Comparative Ex.                     E.sub.1                                                                           10.6                                                                             (12)                                                                              "         126 0.02 87     0.07 Comparative Ex.                     F.sub.1                                                                           21.9                                                                             (25)                                                                              "         126 0.02 77     0.03 Comparative Ex.                     __________________________________________________________________________        Silver Cyanine dye (during                                                    Bromide                                                                              recrystallization) Pressure De-                                                                         Pressure                                 Sample                                                                            (g) (mols %)                                                                         (mol/mol Ag)                                                                            Speed                                                                             Fogging                                                                            sensitization                                                                        Fogging                                                                            Remarks                             __________________________________________________________________________    A.sub.2                                                                           6.9                                                                              (5) --        97  0.02 94     0.33 Comparative Ex.                     B.sub.2                                                                           6.9                                                                              (5) D-29 (3 × 10.sup.-4 )                                                             123 0.02 100    0.04 This Invention                      C.sub.2                                                                           0.3                                                                              (0.2)                                                                             "         77  0.02 100    0.41 Comparative Ex.                     D.sub.2                                                                           0.95                                                                             (0.7)                                                                             "         107 0.02 100    0.13 This Invention                      E.sub.2                                                                           16.7                                                                             (12)                                                                              "         129 0.02 92     0.05 This Invention                      F.sub.2                                                                           34.6                                                                             (25)                                                                              "         126 0.02 88     0.03 Comparative Ex.                     __________________________________________________________________________

The speed is shown as a relative value of the reciprocal of the exposurerequired to provide a density of fog +0.5, the value obtained for sampleA₁ being taken to be 100. Pressure desensitization is indicated for eachsample as the change in density in the folded region when the coatedsample had been folded through 90° C. prior to exposure and development,the relative value of density 0.3 being taken to be 100. Pressurefogging is indicated by the density of a part of the coated sample whichhad been folded through 45° C.

On comparing the results obtained with samples A₁ to F₁ where halogenexchange had been carried out with the addition of potassium bromidewith the results obtained with samples A₂ to F₂ where recrystallizationhad been carried out using an equimolar amount of silver bromide it isclear that the samples obtained with the addition of silver bromide wereall better with respect to pressure desensitization and pressure fogging

Moreover, of the samples A₂ to F₂, the sample A₂ in which an emulsionwhich had been recrystallized in the absence of cyan dye was used wasliable to both pressure desensitization and pressure fogging, while withsample B₂ of this invention there was a clear improvement in performancewith an increase in speed and, moreover, a reduction of both pressuredesensitization and pressure fogging.

Even when the cyanine dye was present, the speed was reduced when theextent of recrystallization was small, and although pressuredesensitization did not occur, pressure fogging occurred easily.Furthermore, the speed was high when a large amount of recrystallizationhad been carried out and there was no pressure fogging, but veryconsiderable pressure desensitization occurred under these conditions.It is clear that the samples of this invention were such that bothpressure desensitization and pressure fogging were suppressed to levelswhere they did not become a problem in practical terms.

EXAMPLE 2

Lime treated gelatin (30 grams) was added to 1000 cc of distilled waterand, after dissolving at 40° C., 6.5 grams of sodium chloride was addedand the temperature was raised to 70° C. A solution obtained bydissolving 62.5 grams of silver nitrate in 750 cc of distilled water anda solution obtained by dissolving 21.9 grams of potassium bromide and10.8 grams of sodium chloride in 500 cc of distilled water were addedto, and mixed with, the aforementioned solution over a period of 40minutes while maintaining the temperature at 70° C. Next, a solutionobtained by dissolving 62.5 grams of silver nitrate in 500 cc ofdistilled water and a solution obtained by dissolving 21.9 grams ofpotassium bromide and 10.8 grams of sodium chloride in 300 cc ofdistilled water were added to, and mixed with, the resulting mixtureover a period of 20 minutes while maintaining the temperature at 75° C.

A solution obtained by dissolving 3.5 grams of potassium bromide in 50cc of distilled water was added 5 minutes after the completion of theaddition described above and, after stirring for a further period of 5minutes, the mixture was desalted and washed, 4.8 mg of sodiumthiosulfate was added and the emulsion was ripened for 40 minutes at 60°C. After adding the aforementioned sensitizing dye D-30 (3×10⁻⁴ mol/molof silver) to this emulsion (variation coefficient 0.12) it was coatedonto a cellulose triacetate base in such a way that the coated weight ofsilver was 2.3 g/m₂ and the coated weight of gelatin was 3.3 g/m₂ toprovide sample G₁.

Moreover, D-30 was added before coating at the rates of 2.25×10⁻⁴,1.5×10⁻⁴, or 0 mol per mol of silver to emulsions prepared in the sameway as before except that sensitizing dye D-30 had been added at therate of 0.75×10⁻⁴, 1.5×10⁻⁴, or 3×10⁻⁴, mol per mol of silver before 5minutes of the completion of the addition of the silver nitrate andsilver halide on the second occasion when preparing the emulsion used inthe production of the sample G₁, and these emulsions were coated onto acellulose triacetate base in the same quantities as for sample G₁ toprovide samples H₁, I₁ and J₁. Emulsions were then prepared by adding anemulsion (gelatin content 50 g/kg, silver bromide content 122

g/kg, average grain size 0.06 μ, variation coefficient 0.07, irridiumcontent 2.4×10⁻⁵ mol per mol of silver) which contained an equimolaramount of silver bromide and irridium bromide mixed crystals in place ofthe potassium bromide which has added after 5 minutes in the preparationof the emulsions used in samples G₁ to J₁, and these emulsions were usedto prepare the corresponding samples G₂ to J₂ in the same way as before.These samples were exposed and processed in the same way as in Example 1and the results obtained were as shown in Table 2. The speeds areindicated as relative values with respect to that of sample G₁ which wastaken to be 100.

                                      TABLE 2                                     __________________________________________________________________________        Potassium                                                                            Cyanine dye (during                                                    bromide                                                                              exchange)          Pressure De-                                                                         Pressure                                 Sample                                                                            (g) (mol %)                                                                          (mol/mol Ag)                                                                            Speed                                                                             Fogging                                                                            sensitization                                                                        Fogging                                                                            Remarks                             __________________________________________________________________________    G.sub.1                                                                           3.5 (4)                                                                              --        100 0.02 83     0.63 Comparative Ex.                     H.sub.1                                                                           "      D-30 (0.75 × 10.sup.-4)                                                           115 0.02 93     0.26 Comparative Ex.                     I.sub.1                                                                           "      D-30 (1.5 × 10.sup.-4)                                                            121 0.02 95     0.14 Comparative Ex.                     J.sub.1                                                                           "      D-30 (3 × 10.sup.-4)                                                              123 0.02 97     0.08 Comparative Ex.                     __________________________________________________________________________        Silver Cyanine dye (during                                                    bromide                                                                              recrystallization) Pressure De-                                                                         Pressure                                 Sample                                                                            (g) (mol %)                                                                          (mol/mol Ag)                                                                            Speed                                                                             Fogging                                                                            sensitization                                                                        Fogging                                                                            Remarks                             __________________________________________________________________________    G.sub.2                                                                           5.5 (4)                                                                              --         97 0.02 89     0.48 Comparative Ex.                     H.sub.2                                                                           5.5 (4)                                                                              D-30 (0.75 × 10.sup.-4)                                                           115 0.02 95     0.19 This Invention                      I.sub.2                                                                           "      D-30 (1.5 × 10.sup.-4)                                                            118 0.02 100    0.10 This Invention                      J.sub.2                                                                           "      D-30 (3 × 10.sup.-4)                                                              121 0.02 100    0.06 This Invention                      __________________________________________________________________________

It is clear from these results that the samples in which emulsions whichhad been recrystallized with silver bromide were used were better inrespect of pressure desensitization and pressure fogging than those inwhich the emulsions where halogen exchange had been carried out usingpotassium bromide, and this effect was especially pronounced in caseswhere the recrystallization had been carried out in the presence ofcyanine dye. Furthermore, it has been confirmed that the reciprocity lawcharacteristics were improved by the inclusion of the irridium salt inthe samples of this invention and that the latent image storageproperties were also improved.

EXAMPLE 3

Lime treated gelatin (30 grams) was added to 1000 cc of distilled waterand, after dissolving at 40° C., 6.5 grams of sodium chloride was addedand the temperature was raised to 75° C. A solution obtained bydissolving 62.5 grams of silver nitrate in 750 cc of distilled water anda solution obtained by dissolving 35.0 grams of potassium bromide and4.3 grams of sodium chloride in 500 cc of distilled water were added to,and mixed with, the aforementioned solution over a period of 40 minuteswhile maintaining the temperature at 80° C. Next, a solution obtained bydissolving 62.5 grams of silver nitrate in 500 cc of distilled water anda solution obtained by dissolving 26.3 grams of potassium bromide and8.6 grams of sodium chloride in 300 cc of distilled water were added to,and mixed with, the resulting mixture over a period of 20 minutes whilemaintaining the temperature at 70° C.

Similar samples to A₁ to F₁ and A₂ to F₂ were prepared using thisemulsion by carrying out halogen exchange with potassium bromide orrecrystallization with silver bromide in the presence of the sensitizingdye D-29 in the same way as in Example 1. These examples were tested inthe same way as in Example 1 and the results obtained indicated that thesamples of this invention had good pressure characteristics.

EXAMPLE 4

Samples K₁ and K₂ were prepared by coating without the addition ofsensitizing dye to the emulsions used when preparing samples A₁ and A₂in Example 1. Similarly samples L₁ to T₁, L₂ to T₂ to which nosensitizing dye had been added were prepared in the same way except thatthe sensitizing dye added during the preparation of emulsions B₁ and B₂was changed from D-29 to the sensitizing dye indicated in Table 3, andthe results obtained on exposing and processing these samples in thesame way as in Example 1 are as shown in Table 3. However, in thisexample direct comparison of speed was of no significance since the typeof sensitizing dye differed, and so only the pressure desensitizationand pressure fogging characteristics have been compared

The pressure desensitization of each sample is indicated as the relativespeed when the speed of the sample when no pressure had been applied wastaken to be 100.

                  TABLE 3                                                         ______________________________________                                             Cyanine dye  Pressure                                                    Sam- (Amount added)                                                                             desensi- Pressure                                           ple  (mol/mol Ag) tization Fogging                                                                              Remarks                                     ______________________________________                                        K.sub.1                                                                            --           82       0.36   Comparative Ex.                             K.sub.2                                                                            --           87       0.13   "                                           L.sub.1                                                                            D-22 (1 × 10.sup.-4)                                                                 92       0.18   "                                           L.sub.2                                                                            "            95       0.15   This Invention                              M.sub.1                                                                            D-22 (3 × 10.sup.-4)                                                                 96       0.13   Comparative Ex.                             M.sub.2                                                                            "            98       0.11   This Invention                              N.sub.1                                                                            D-22 (6 × 10.sup.-4)                                                                 92       0.11   Comparative Ex.                             N.sub.2                                                                            "            93       0.08   This Invention                              O.sub.1                                                                            D-24 (3 × 10.sup.-4)                                                                 97       0.15   Comparative Ex.                             O.sub.2                                                                            "            97       0.12   This Invention                              P.sub.1                                                                            D-30 (3 × -4)                                                                        96       0.08   Comparative Ex.                             P.sub.2                                                                            "            97       0.06   This Invention                              Q.sub.1                                                                            D-36 (3 × 10.sup.-4)                                                                 94       0.09   Comparative Ex.                             Q.sub.2                                                                            "            96       0.06   This Invention                              R.sub.1                                                                            D-97 (8 × 10.sup.5)                                                                  88       0.22   Comparative Ex.                             R.sub.2                                                                            "            92       0.18   This Invention                              S.sub. 1                                                                           D-101 (8 × 10.sup.-5)                                                                86       0.23   Comparative Ex.                             S.sub.2                                                                            "            88       0.18   This Invention                              T.sub.1                                                                            D-102 (8 × 10.sup.-5)                                                                89       0.21   Comparative Ex.                             T.sub.2                                                                            "            91       0.16   This Invention                              ______________________________________                                    

The samples prepared using emulsions which had been recrystallized usingsilver bromide in the presence of a sensitizing dye gave better resultsin which both pressure desensitization and pressure fogging werereduced.

EXAMPLE 5

Samples were prepared in the same way as samples L2 to T2 but changingthe silver bromide emulsion used for recrystallization of each of theemulsions prepared in Example 4 in the preparation of samples L₂ to T₂to a silver chlorobromide emulsion (gelatin 50 g/kg, silver bromidecontent 70 mol %, silver chloride content 30 mol %, total silver halidecontent 113 g/kg, average grain size 0.065 μ, variation coefficient0.07) and the results obtained indicated that the samples correspondingto samples M₂ to T₂ had similarly excellent pressure characteristics.

EXAMPLE 6

Four types of emulsions were prepared using silver bromide/irridiumhexachloride mixed crystals (average grain size 0.06 μ, variationcoefficient 0.07, irridium content 2.4×10⁻⁵ mol per mol of silver) orsilver bromide/rhodium bromide mixed crystals (average grain size 0.06μ, variation coefficient 0.07, rhodium content 2×10⁻⁶ mol per mol ofsilver) respectively in place of the silver bromide/irridium bromidemixed crystals used in the preparation of the emulsions used in Example2. In the former case results virtually the same as those obtained usingthe emulsions of Example 2 were obtained, but the performance of theemulsions corresponding to emulsions H₂, I₂ and J₂ were superior inrespect of pressure characteristics and reciprocity law characteristics.In the latter case the results were different from those obtained withthe emulsions in Example 2 but the emulsions of this invention wereparticularly good in respect of their pressure characteristics and thehardness of the gradation.

EXAMPLE 7

Multi-layer color printing papers of which the layer structure was shownin table 9 were prepared on a paper support which had been laminated onboth sides with polyethylene.

First Layer Coating Liquid

Ethyl acetate (27.2 cc) and 7.9 cc of solvent (c) were added to 22.0grams of yellow coupler (a) and 3.9 grams of the colored imagestabilizer (b) to form a solution and this solution was emulsified anddispersed in 185 cc of 10% aqueous gelatin solution which contained 8 ccof 10% sodium dodecylbenzenesulfonate. On the other hand, the bluesensitive sensitizing dye indicated below was added at the rate of5.0×10⁻⁴ mol per mol of silver to a silver chlorobromide emulsion(silver bromide content 80 mol %, average grain size 0.81 μ, variationcoefficient 0.10, cubic form) to provide an emulsion. The abovementioned emulsified dispersion and the emulsion were mixed together toform a solution and the first layer coating liquid of which thecomposition is shown in Table 4 was prepared. The coating liquids forthe second to the seventh layers were prepared in the same way as thecoating liquid for the first layer, and the composition of the second toseventh layers are shown in Table 4. Moreover,1-oxy-3,5-dichloro-s-triazine, sodium salt, was added to each layer as agelatin hardening agent.

The emulsions A₁ to F₁ and A₂ to F₂ prepared in Example 1 and theemulsions G₁ to J₁ and G₂ to J₂ prepared in Example 2 were used for theemulsion used for the green sensitive layer. Dye was added in the sameway as in each example, the addition being made at the time of coatingin the case of the emulsions A₁, A₂, G₁ to I₁₁, G₂ to I₂. These samplesare referred to sequentially as samples u₁ to u₁₂ and v₁ to v₈.

The spectrally sensitizing dyes indicated below were used for each layerother than the green sensitive emulsion layer.

    ______________________________________                                        Blue Sensitive Emulsion Layer                                                 D-24                                                                          (5.0 × 10.sup.-4 mol per mol of silver halide)                          Red Sensitive Emulsion Layer                                                  D-97                                                                          (0.8 × 10.sup.-4 mol per mol of silver halide)                          ______________________________________                                    

Moreover, 4-hydroxy-6-methyl-1,3,3a,7-tetra-azaindene was added asstabilizer and 1-(m-methyl- ureido)phenyl-5-mercaptotetrazole was addedas an antifogging agent to each of the emulsion layers. Furthermore,2-amino-5-mercapto-1,3,4-thiadiazole and4,4'-bis(dinaphthoxypyrimidinylamino)stilbene-2,2'-sulfonic acid, (0.006mg/m²) were added to the red sensitive layer.

The dyes indicated below were added to the emulsion layers foranti-irradiation purposes. ##STR45##

The structural formulae of the compounds such as the couplers etc. usedin this example indicated below. ##STR46##

                                      TABLE 4                                     __________________________________________________________________________                                             Amount Used                          Layer       Principal Composition        (g/m.sup.2)                          __________________________________________________________________________    Seventh layer                                                                             Gelatin                      1.33                                 (Protective layer)                                                                        Acrylic modified poly(vinyl alcohol) 17% modification                                                      0.17                                 Sixth layer Gelatin                      0.54                                 (UV absorbing layer)                                                                      Ultraviolet absorber (h)     0.20                                             Solvent (j)                  0.09 cc                              Fifth layer Silver chlorobromide emulsion (silver bromide content                                                      0.24                                 (Red sensitive layer)                                                                     mol %, 0.45μ , variation coefficient 0.12, cubic)                          Gelatin                      1.62                                             Cyan coupler (k)             0.38                                             Colored image stabilizer (b) 0.46                                             Colored image stabilizer (l) 0.17                                             Colored image stabilizer (m) 0.03                                             Solvent (c)                  0.23 cc                              Fourth layer                                                                              Gelatin                      1.60                                 (UV absorbing layer)                                                                      Ultraviolet absorber (h)     0.60                                             Anti-color mixing agent (d)  0.05                                             Solvent (j)                  0.26 cc                              Third layer Silver chlorobromide emulsion A.sub.1 -F.sub.1, A.sub.2                       -F.sub.2, G.sub.1 -J.sub.1, G.sub.2 -J.sub.2                                                               0.18                                 (Green sensitive layer)                                                                   Gelatin                      1.80                                             Magenta coupler (e)          0.35                                             Colored image stabilizer (f) 0.20                                             Colored image stabilizer (m) 0.10                                             Colored image stabilizer (n) 0.07                                             Solvent (g)                  0.45 cc                              Second layer                                                                              Gelatin                      0.99                                 (Anti-color mixing                                                                        Anti-color mixing agent (d)  0.08                                 layer)      Solvent (j)                  0.09 cc                              First layer Silver chlorobromide emulsion (silver bromide content                                                      0.27                                 (Blue sensitive layer)                                                                    mol %, 0.81μ , variation coefficient 0.10, cubic)                          Gelatin                      1.86                                             Yellow coupler (a)           0.85                                             Colored image stabilizer (b) 0.15                                             Solvent (c)                  0.31 cc                              Support     Polyethylene laminated paper (TiO.sub.2 (3.0 g/m.sup.2) and                   ultramarine were included in the polyethylene on the first                    layer side)                                                       __________________________________________________________________________     The chlorobromide emulsions are indicated in terms of the weight              calculated as silver.                                                    

These samples were subjected to pressure by folding and then they areexposed for 0.5 seconds through an optical wedge, after which they wereprocessed in the way indicated below. The results obtained were as shownin Table 5.

    ______________________________________                                        Processing                                                                                   Temperature                                                    Process        (°C.)   Time                                            ______________________________________                                        Color development                                                                            37             3 min. 30 sec.                                  Bleach-fix     33             1 min. 30 sec.                                  Water wash     24 to 34       3 min.                                          Drying         80             1 min.                                          ______________________________________                                    

The compositions of the processing baths were as indicated below.

    ______________________________________                                        Color Development Bath                                                        ______________________________________                                        Water                  800         ml                                         Diethylenetriamine penta-acetic acid                                                                 3.0         g                                          Benzyl alcohol         15          ml                                         Diethyleneglycol       10          ml                                         Sodium sulfite         2.0         g                                          Potassium bromide      1.0         g                                          Potassium carbonate    30.0        g                                          N-Ethyl-N-(β-methanesulfonamidoethyl)-                                                          4.5         g                                          3-methyl-4-aminoaniline sulfate                                               Hydroxylamine sulfate  4.0         g                                          Fluorescent whitener (4,4'-diamino-                                                                  1.0         g                                          stilbene based)                                                               Water                  to make up to                                                                 1000        ml                                         pH (25° C.)     10.10                                                  Bleach-fix Bath                                                               Water                  400         ml                                         Ammonium thiosulfate (70% solution)                                                                  150         ml                                         Sodium sulfite         18          g                                          Ethylenedamine tetra-acetic acid,                                                                    55          g                                          iron(III) ammonium salt                                                       Ethylenediamine tetra-acetic acid,                                                                   5           g                                          disodium salt                                                                 Water                  to make up to                                                                 1000        ml                                         pH (25° C.)     6.70                                                   Water Wash Bath                                                               Ion exchanged water (Ca++, Mg++ each about 1 ppm)                             ______________________________________                                    

Speed was taken to be the reciprocal of the exposure required to give adensity of fog +1.0.

The numerical values for the samples u₁ to u₁₂ represent relative valuestaking the value for sample u₁ to be 100. The numerical values forsamples v₁ to v₈ are relative values taking the value for v₁ to be 100.

Gamma represents the slope of a straight line joining densities of 0.8and 1.8.

Pressure desensitization is represented by the change in density at thepoint of fog +1.0 relative to the density when no pressure had beenapplied.

It is clear from the results shown in table 5 that the samples of thisinvention were superior overall in respect of speed, gamma and pressurecharacteristics.

                  TABLE 5                                                         ______________________________________                                                                  Pressure                                            Sam-         Fog-         Desensi-                                                                             Pressure                                     ple  Speed   ging   Gamma tization                                                                             Fogging                                                                              Remarks                               ______________________________________                                        u.sub.1                                                                            100     0.08   1.90   97    0.25   Comparative                                                                   Example                               u.sub.2                                                                            116     0.08   2.44  100    0.08   Comparative                                                                   Example                               u.sub.3                                                                             85     0.08   2.40  100    0.29   Comparative                                                                   Example                               u.sub.4                                                                            103     0.08   2.37  100    0.09   Comparative                                                                   Example                               u.sub.5                                                                             80     0.08   2.49   94    0.08   Comparative                                                                   Example                               u.sub.6                                                                            120     0.08   2.49   90    0.08   Comparative                                                                   Example                               u.sub.7                                                                             97     0.08   2.13   98    0.13   Comparative                                                                   Example                               u.sub.8                                                                            120     0.08   2.90  100    0.08   This                                                                          Invention                             u.sub.9                                                                            80      0.08   2.38  100    0.17   Comparative                                                                   Example                               u.sub.10                                                                           107     0.08   2.47  100    0.08   This                                                                          Invention                             u.sub.11                                                                           126     008    2.81   97    0.08   This                                                                          Invention                             u.sub.12                                                                           126     0.08   2.63   95    0.08   Comparative                                                                   Example                               v.sub.1                                                                            100     0.08   2.22   92    0.38   Comparative                                                                   Example                               v.sub.2                                                                            107     0.08   2.39   98    0.11   Comparative                                                                   Example                               v.sub.3                                                                            115     0.08   2.48  100    0.08   Comparative                                                                   Example                               v.sub.4                                                                            120     0.08   2.63  100    0.08   Comparative                                                                   Example                               v.sub.5                                                                             93     0.08   2.32   96    0.22   Comparative                                                                   Example                               v.sub.6                                                                            110     0.08   2.46  100    0.09   This                                                                          Invention                             v.sub.7                                                                            112     0.08   2.73  100    0.08   This                                                                          Invention                             v.sub.8                                                                            121     0.08   2.85  100    0.08   This                                                                          Invention                             ______________________________________                                    

EXAMPLE 8

Samples in which the red sensitive emulsion in the samples prepared inExample 7 was replaced by the emulsions R₁, S₁, T₁, S₂, T₂ used inExample 4 were prepared. The samples in which the emulsions R₂, S₂ andT₂ had been used had superior pressure characteristics and hardness ofgradation.

EXAMPLE 9

Samples in which the emulsions used in the green sensitive layer of thesamples prepared in Example 7 and the amounts of silver coated weremodified in the way indicated below were prepared

    ______________________________________                                        Silver chlorobromide emulsion (u.sub.1 to u.sub.12,                                                   0.32 g/m.sup.2                                        v.sub.1 to v.sub.8)                                                           Gelatin                 1.45 g/m.sup.2                                        Magenta coupler (o)     0.32 g/m.sup.2                                        Colored image stabilizer (p)                                                                          0.07 g/m.sup.2                                        Colored image stabilizer (f)                                                                          0.13 g/m.sup.2                                        Colored image stabilizer (q)                                                                          0.03 g/m.sup.2                                        Colored image stabilizer (r)                                                                          0.10 g/m.sup.2                                        Solvent (g)             0.43 g/m.sup.2                                        ______________________________________                                    

These samples were tested in the same way as in Example 7 and thesamples of this invention were superior, exhibiting the same trends asbefore. ##STR47##

EXAMPLE 10

The samples used in Examples 7, 8 and 9 were processed in the wayindicated below. Similar results were obtained in respect of pressurecharacteristics.

    ______________________________________                                        Processing                                                                                   Temperature                                                    Process        (°C.)   Time                                            ______________________________________                                        Color development                                                                            37             3 min. 30 sec.                                  Bleach-fix     33             1 min. 30 sec.                                  Water wash     24 to 34       3 min.                                          Drying         80             1 min.                                          ______________________________________                                    

The compositions of the processing baths were as indicated below.

    ______________________________________                                        Color Development Bath                                                        ______________________________________                                        Water                 800         ml                                          Ethylenediamine-N,N,N',N'- tetra-                                                                   1.5         g                                           ethylenephosphonic acid                                                       Triethanol            4           cc                                          1,4-Diazabicyclo[2,2,2]octane                                                                       3           g                                           N,N-Diethylhydroxylamine oxalate                                                                    3           g                                           Potassium bromide     1.0         g                                           Potassium carbonate   30.0        g                                           N-Ethyl-N-(β-methanesulfonamido-                                                               4.5         g                                           ethyl)-3-methyl-4-aminoaniline sulfate                                        N,N-Bis(carboxymethyl)hydrazine                                                                     4.0         g                                           Fluorescent whitener (4,4'-diamino-                                                                 1.0         g                                           stilbene based)                                                               Water                 to make up to 1000                                                                        ml                                          pH (25° C.)    10.10                                                   Bleach-fix Bath                                                               Water                 400         ml                                          Ammonium thiosulfate (70% solution)                                                                 150         ml                                          Sodium sulfite        18          g                                           Ethylenediamine tetra-acetic acid,                                                                  55          g                                           iron(III) ammonium salt                                                       Ethylenediamine tetra-acetic acid,                                                                  5           g                                           disodium salt                                                                 Ammonium bromide      20          g                                           Water                 to make up to 1000                                                                        ml                                          pH (25° C.)    6.70                                                    Water Wash Bath                                                               Ion exchanged water (Ca++, Mg++ each about 1 ppm)                             ______________________________________                                    

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A silver halide photographic material comprisinga support having thereon at least one emulsion layer containing anessentially silver iodide free silver chloride, silver bromide or silverchlorobromide emulsion obtained: (1) by recrystallization of from 0.3 to15 mol % of total silver halide using fine crystals of a sparinglysoluble bromide, chloride or chlorobromide under conditions in which atleast one of a simple cyanine dye, a carbocyanine dye or adicarbocyanine dye is present on the surface of the silver halide grainsin a silver halide emulsion which has a grain size distribution suchthat the variation coefficient is not more than 0.25, and (2) bychemical sensitization.
 2. The silver halide photographic materialclaimed in claim wherein the sparingly soluble bromides, chlorides orchlorobromides have a solubility of not more than 1 gram in 100 grams ofwater at 20° C.
 3. The silver halide photographic material claimed inclaim 2, wherein the solubility is not more than 0.2 gram in 100 gramsof water at 20° C.
 4. The silver halide photographic material claimed inclaim 1, wherein the recrystallization is from 0.6 to 12 mol %.
 5. Thesilver halide photographic material claimed in claim I, wherein therecrystallization is from 0.6 to 9 mol %.
 6. The silver halidephotographic material claimed in claim 1, wherein the recrystallizationis from 0.6 to 6 mol %.
 7. The silver halide photographic materialclaimed in claim 1, wherein the simple cyanine dye, carbocyanine ordicarbocyanine dye is represented by the formula (I) ##STR48## Wherein Lrepresents a methine group or a substituted methine group, R₁ and R₂each represents an alkyl or a substituted alkyl group, Z₁ and Z₂ eachrepresents a group of atoms which forms a nitrogen containing 5 or 6membered heterocyclic nucleus, X represents an anion, n represents 1, 3or 5, n₁ and n₂ represent 1 or 2, provided that n₁ =n₂ =0 when n=5 andthat n₁ or n₂ =0 when n=3, and m represents 0 or 1, provided that mrepresents 0 when an intramolecular salt is formed, and further providedthat when n is 5, the groups represented by L can be joined together toform a substituted or unsubstituted 5 or 6 membered ring.
 8. The silverhalide photographic material claimed in claim 7, wherein R₁ and R₂ eachrepresents an ethyl group, a propyl group, a butyl group, a pentylgroup, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, anda sulfopentyl group.
 9. The silver halide pholographic material claimedin claim 7, wherein Z₁ and Z₂ each represents a substituted benzoxazolenucleus, a substituted benzothiazole nucleus, and a substitutedbenzoselenazole nucleus.
 10. The silver halide photographic materialclaimed in claim 7, wherein X represents a bromine ion, an iodine ion,and a p-toluenesulfonic acid anion.
 11. The silver halide photographicmaterial claimed in claim 1, wherein the variation coefficient is notmore than 0.20.
 12. The silver halide photographic material claimed inclaim 11, wherein the variation coefficient is not more than 0.15. 13.The silver halide photographic material claimed in claim 12, wherein thevariation coefficient is not more than 0.10.
 14. The silver halidephotographic material claimed in claim 1, wherein the chemicalsensitization comprises sulfur sensitization.
 15. The silver halidephotographic material claimed in claim 1, wherein said sparingly solublebromide, chloride or chlorobromide is selected from the group consistingof an iridium salt, a gold salt, a mercury salt, a thallium salt, acopper salt, a lead salt, a platinum salt, a palladium salt, and arhodium salt.
 16. The silver halide photographic material claimed inclaim 1, wherein said sparingly soluble bromide, chloride orchlorobromide is a mixed crystal of a silver salt with at least one saltconsisting of an iridium salt, a gold salt, a mercury salt, a thalliumsalt, a copper salt, a lead salt, a platinum salt, a palladium salt, anda rhodium salt.
 17. The silver halide photographic material claimed inclaim 1, wherein said fine crystal is a sparingly soluble chlorobromideand the surface of the silver halide grain which is subjected torecrystallization is a silver chlorobromide.
 18. The silver halidephotographic material claimed in claim 15, wherein said fine crystal isa sparingly soluble chlorobromide and the surface of the silver halidegrain which is subjected to recrystallization is a silver chlorobromide.19. The silver halide photographic material claimed in claim 1, whereinsaid fine crystal is a sparingly soluble chlorobromide and the surfaceof the silver halide grain which is subjected to recrystallization is asilver chloride
 20. The silver halide photographic material claimed inclaim 15, wherein said fine crystal is a sparingly soluble chlorobromideand the surface of the silver halide grain which is subjected torecrystallization is a silver chloride
 21. The silver halidephotographic material claimed in claim 1, wherein said fine crystal is asparingly soluble bromide and the surface of the silver halide grainwhich is subjected to recrystallization is a silver chlorobromide. 22.The silver halide photographic material claimed in claim 15, whereinsaid fine crystal is a sparingly soluble bromide and the surface of thesilver halide grain which is subjected to recrystallization is a silverchlorobromide.
 23. The silver halide photographic material claimed inclaim 1, wherein said fine crystal is a sparingly soluble chloride andthe surface of the silver halide grain which is subjected torecrystallization is a silver chloride or a silver chlorobromide. 24.The silver halide photographic material claimed in claim 15, whereinsaid fine crystal is a sparingly soluble chloride and the surface of thesilver halide grain which is subjected to recrystallization is a silverchloride or a silver chlorobromide.
 25. The silver halide photographicmaterial claimed in claim 1, wherein the difference between the silverbromide content of the silver halide grain which is subjected torecrystallization and the bromide content of the sparingly soluble finecrystal is at least 10 mol %.
 26. The silver halide photographicmaterial claimed in claim 15, wherein the variation coefficient of saidemulsion is not more than 0.15.
 27. The silver halide photographicmaterial claimed in claim 16, wherein the variation coefficient of saidemulsion is not more than 0.15.
 28. The silver halide photographicmaterial claimed in claim 7, wherein said nitrogen containingheterocyclic nuclei formed by Z₁ or Z₂ include an oxazole nucleus, athiazole nucleus, a selenazole nucleus, an imidazole nucleus, a pyridinenucleus, an oxazoline nucleus, a thiazoline nucleus, a selenazolinenucleus, an imidazoline nucleus and those nuclei in which these nucleiare condensed with a benzene ring, a naphthalene ring or other saturatedor unsaturated carbocyclic ring, and a substituent group can be bondedonto these heterocyclic rings as a substituent group.